3.

22 Structure and Mechanics of Materials

Class 18: Amorphous Materials

Frances M. Ross and Ming Dao

Ting Yang

Massachusetts Institute of Technology

Department of Materials Science and Engineering
fmross@mit.edu; mingdao@mit.edu
 The structure of amorphous materials

What is different between an amorphous material and a crystalline one?

Why do amorphous materials form?

Examples of amorphous materials

 The structure of amorphous materials

What is different between an amorphous material and a crystalline one?

Density of the packing

Energy per atom
Unsatisfied bonds
Order at long, medium, short length scales
Translational symmetry

Why do amorphous materials form?

Examples of amorphous materials

 The structure of amorphous materials

What is different between an amorphous material and a crystalline one?

Density of the packing

Energy per atom
Unsatisfied bonds
Order at long, medium, short length scales
Translational symmetry

Why do amorphous materials form?

Too much disorder to crystallize (polymers)
Rapid cooling (metals)

Examples of amorphous materials

 The structure of amorphous materials

What is different between an amorphous material and a crystalline one?

Density of the packing

Energy per atom
Unsatisfied bonds
Order at long, medium, short length scales
Translational symmetry

Why do amorphous materials form?

Too much disorder to crystallize (polymers)
Rapid cooling (metals)

Examples of amorphous materials

Amorphous silicon
Covalent network glass (silicates) What is the difference between an
Metallic glass
Polymers (rubbery or glassy)
amorphous material and a glass?
Amorphous materials in technology

Glass cover
Camera lens
TFT display
Dielectrics
Circuit packaging
Metallic glass case
Phase change memory
Solid state battery

Gorilla glass: replace Na with K, creates compressive stress that closes cracks

Thanks JJ for these slides!

Types and applications of amorphous materials

Thanks Silvija for these slides!

 Phase change materials

Blu-Ray disc

Thanks Silvija for these slides!

 The transition between amorphous and crystalline

Amorphous to 40nm Sb3.6Te on a silicon nitride

crystalline membrane, at 85°C
transformation Kooi and de Hosson 2004
in phase
change
materials
as seen in TEM beam-induced crystallization of
an amorphous data mark in
14nm Ga15Sb85

CD-RW/DVD1RW disk consisting

of ZnS:SiO2/GaSb/
ZnS:SiO2/SiN/Ag/SiN on a
polycarbonate substrate. All
layers removed except for the
GaSb and surrounding dielectric
layers. Kaiser et al 2004.
What
about
glass?
What
about
Every day items (cups)
glass? Buildings (windows)
Transport (car windows;
lightweight composites)
Healthcare (glassware,
drug delivery)
Clean energy (wind
vanes, biofuel
production)
Information and
communication (fiber
optics)
Science (lenses)
Art
 Properties of glass

Mechanical properties

Optical properties

Electrical properties

Chemical properties

Natural vs. man made

Metallic glass

Galileo found amorphous ice - NASA Fulgurite - NPS

Thanks JJ for these slides!
 Properties of glass

Mechanical properties Brittle, fragile, stiff?

Optical properties Transparent?

Electrical properties Insulating?

Chemical properties Inert, durable?

Natural vs. man made Obsidian, fulgurite, amorphous ice on Jupiter’s moons

Metallic glass

Galileo found amorphous ice - NASA Fulgurite - NPS

Thanks JJ for these slides!
 The structure of amorphous materials

What is different between an amorphous material and a crystalline one?

Density of the packing

Energy per atom
Unsatisfied bonds
Order at long, medium, short length scales
Translational symmetry

Why do amorphous materials form?

Too much disorder to crystallize (polymers)
Rapid cooling (metals)

Examples of amorphous materials

Amorphous silicon
Covalent network glass (silicates) What is the difference between an
Metallic glass
Polymers (rubbery or glassy)
amorphous material and a glass?
 What is a glass?
Cool from liquid
state to find out

Glass: the state of a material below

the glass transition
do not crystallize, just change slope
of specific volume at Tg

At Tg, kT is too low to reach lowest

Crystal: sharp energy state
liquid to solid
transformation Lock into a solid state with high
viscosity; state depends on cooling
rate

Debenedetti and Stillinger, Nature 2001

 What is a glass?
Cool from liquid
state to find out

Glass: the state of a material below

the glass transition
do not crystallize, just change slope
of specific volume at Tg

At Tg, kT is too low to reach lowest

Crystal: sharp energy state
liquid to solid
transformation Lock into a solid state with high
viscosity; state depends on cooling
rate

Debenedetti and Stillinger, Nature 2001

 Supercooled liquid vs. glass

Think about these aspects of the supercooled liquid state and the glass state:

Structure

Conditions of formation

Behavior (e.g. viscosity)

Can molecules rearrange as T is reduced?

 What is a glass?

A metastable state with no long range order and exhibiting a glass transition

A non-equilibrium, non-crystalline state of a material that exhibits a glass transition. The structure is similar to the
supercooled liquid. Eventually it crystallizes.

Zanotto and Mauro, The glassy state of matter: Its definition and ultimate fate, J. Non-Cryst. Solids 471, 490 (2017)

The objective of this communication is to clarify the meanings of solid and liquid, to dwell on the ultimate fate of
glass in the limit of infinitely long time, and to propose a modern, improved definition of glass. We review the four
characteristic states of matter related to vitrification: the stable equilibrium liquid (L), the metastable supercooled
liquid (SCL), the unstable nonequilibrium glass (G), and the stable crystal (C). We also discuss some relevant terms
and phenomena, including glass transition, crystallization, non-crystalline, amorphous, solid, and frozen. We review
several previously published definitions of glass and finally propose an improved definition in two alternative forms.
The first improved definition is: “Glass is a nonequilibrium, non-crystalline state of matter that appears solid on a
short time scale but continuously relaxes towards the liquid state.” This is an intuitive description for the general
public and young students. An alternative, more detailed definition to be understood and used by advanced students,
researchers, and professors is: “Glass is a nonequilibrium, non-crystalline condensed state of matter that exhibits a
glass transition. The structure of glasses is similar to that of their parent supercooled liquids (SCL), and they
spontaneously relax toward the SCL state. Their ultimate fate, in the limit of infinite time, is to crystallize.” This
definition is for experts who understand the meaning of glass transition.
 What is a glass?

A metastable state with no long range order and exhibiting a glass transition

A non-equilibrium, non-crystalline state of a material that exhibits a glass transition. The structure is similar to the
supercooled liquid. Eventually it crystallizes.

Common visual guides to glasses

 The glass transition in more detail

V, H

Liquid When the system is kept

in thermal equilibrium:
 First-order liquid-solid
phase transition
Melting /  Discontinuity of
solidification extensive thermo-
dynamic parameters
(e.g., V and H)
Crystal  Reversible process

Tm T
Thanks JJ for these slides!
 The glass transition in more detail

V, H Supercooled
liquid  Supercooled liquid
transforms to the glassy
Liquid
state when
Glass crystallization is
transition kinetically suppressed
 Extensive variables
remain continuous
Glass during glass transition
 The glassy state is
different from super-
Crystal cooled liquid
 Tf : Fictive temperature

Tf Tm T
Thanks JJ for these slides!
 The glass transition in more detail

V, H Supercooled
liquid  Glasses obtained at
different cooling rates
Liquid have different structures
Increasing  With increasing cooling
cooling rate rate:
 V1 < V2 < V3
Free volume increases
3
 H1 < H2 < H3
2
Configurational entropy
1 increases
 Tf,1 < Tf,2 < Tf,3

Tm T
Thanks JJ for these slides!
 The glass transition in more detail

Supercooled
V liquid

Liquid

The heating curve never

retraces the cooling curve
during glass transition due to
structural relaxation

Tm T
Thanks JJ for these slides!
 Describing the resulting material
Descriptors are quantitative and measurable and are
Two important “descriptors”: statistical for disordered materials
Aim to distinguish between gases, liquids and glasses

Free volume Pair distribution function

 Describing the resulting material
Descriptors are quantitative and measurable and are
Two important “descriptors”: statistical for disordered materials
Aim to distinguish between gases, liquids and glasses

Free volume Pair distribution function

for crystals asymptotic value

for glasses or liquids correlation length
for gases peaks and valleys
change during crystallization

What properties should

this influence?
 The pair distribution function

Pair distribution function (PDF): g(r)

Consider an amorphous material with an average number density of atoms
given by:
 n V n : number of atoms V : material volume

The number density of atoms at a distance r from an origin atom is given by

  g (r )

When r  0, g  0
When r  , g  1

Thanks JJ for these slides!

 The pair distribution function

g(r) 1st coordination shell

2nd coordination shell

In a crystal

g(r)

In a glass
1

r
0
Thanks JJ for these slides!
 Related expressions for pair distribution

Pair correlation function h(r)

h( r )  g ( r )  1

Radial distribution function (RDF): J(r)

J (r )  4 r 2   g (r )
J(r)dr gives the number of atoms located between r and r + dr away from
the origin atom
The area under the RDF curve gives the number of atoms

Reduced radial distribution function (rRDF): G(r)

G (r )  4 r 2    g (r )  1  4 r 2   h(r )

Thanks JJ for these slides!

Which materials make glasses?
 Which materials make glasses?

1. Network glasses 2. Metallic glasses 3. Polymers (others too)

rapid cooling is usually necessary hard to crystallize; glassy

to avoid crystallization state easy to achieve

We can start to appreciate the differences between these glasses if we think about their structure in a
topological way.

Thanks JJ for these slides!

 1. Network glass structure

Short-range order is preserved (AO3 triangles)

Long-range order is disrupted by changing bond
angle (mainly) and bond length

A2O3 crystal A2O3 glass

Random Network Theory

Zachariasen, The Atomic Arrangement in Glass, JACS 1932
Which elements make up network glasses?
Network glasses are not small crystals

Absence of small angle scattering

Continuous structure without micro-
voids and micro-crystals
Broad diffraction peak
Size of ordered region < 8 Å (Scherrer
equation)
Unit cell size of cristobalite: 7.1 Å

Warren and Biscce, J. Am. Cer. Soc. 1938

Thanks JJ for these slides!

 Bond angle flexibility is key to their structure
Si-O-Si bond angle distribution in silica glass measured by XRD
Normalized distribution

Si-O-Si bond-bending constraint

is relaxed at the forming
temperature of silica glass

144°: Si-O-Si bond

angle in a-quartz

Si-O-Si bond angle in fused silica

Mozzi and Warren, J. Appl. Cryst. 1969

Thanks JJ for these slides!

 Testing the random network model

Radial distribution function

For silica glass, excellent agreement between
Evans and King, Nature 1966 XRD and ball-and-stick model constructed
Now in the Science Museum, London according to the random network model

Thanks JJ for these slides!

 Modifying the network

Glass network formers

Form the interconnected backbone glass network
Glass network modifiers
Present as ions to alter the glass network
Compensated by non-bridging oxygen (NBO) in oxide glasses
Usually reduce glass network connectivity
Intermediates
Can function as network formers or modifiers depending on glass composition
 Modifying the network

O O

Silicon:
O Si O Si O Na2O glass former
Sodium:
O O network modifier
Bridging oxygen
Sodium reduces
O O connectivity; what
would boron do?

O Si O- Na+ Na+ O- Si O

O Non-bridging oxygen O

Thanks JJ for these slides!

 Relationship of network connectivity to glass
forming ability

Suppose the network has

too few linkages… Suppose the network has
too many linkages… But what if it’s
just right…

Constraints: for each of the N atoms, the bonds can vary in terms of length and angle.
#Constraints = 2.5r-3 for each atom with r bonds. (Don’t worry about the derivation!)
Degrees of freedom: the coordinates of each atom. #DOF = 3N
Result of this model: an optimal “magic” coordination number <r>=2.4. Choose a composition that achieves this!

See the problem set!

 2. Metallic glass structure

Polycrystalline Amorphous metal

metal

Grain
boundaries

Metallic glass / amorphous metal / glassy metal lacks directional bonding, can be nearly close packed and has
coordination polyhedral similar to crystalline phases, including icosahedral coordination.

Inoue’s empirical rules for bulk metallic glass (BMG) formation

Multicomponent systems consisting of three or more elements
Significant difference in atomic size ratios (frustration)
Negative enthalpy of mixing

Thanks JJ for these slides!

 Dense random packing of hard spheres
This model provides a description of the atomic-
level arrangement of the amorphous metal
Bernal and Finney, Disc. Faraday Society, 1967 The five ‘canonical
holes’ identified by
Bernal in random
sphere packing

Voronoi polyhedra surround each atom.

13 faces, pentagonal. on average!

Bernal’s model - spheres attached with paint

Shows near and farther contacts via paint marks
 Hard sphere packing in 2d and 3d

Dense packing is only achieved at certain critical radius ratios. Dense packing favours glass formation: the
system becomes stuck in a deep energy well as it is cooled.
 Beyond nearest neighbors: cluster packing

Locally close packed clusters form, with atoms of different radius fulfilling different topological roles. The
cluster packing model correctly predicts the atomic size and composition of stable metallic glasses.
 Summary

Network glasses Metallic glasses Polymers (others too)

rapid cooling is usually necessary hard to crystallize; glassy

to avoid crystallization state easy to achieve

We can start to appreciate the differences between these glasses if we think about their structure in a
topological way.

Thanks JJ for these slides!

 Summary

1. Network glasses 2. Metallic glasses 3. Polymers (others too)

rapid cooling is usually necessary hard to crystallize; glassy

to avoid crystallization state easy to achieve

How do the concepts of mechanical deformation that we discussed for crystals work out for amorphous
solids, including glasses?